Method for utilizing bisphosphorylated imidodi-thicarbonates as insecticides or arachnicides

ABSTRACT

Bis-N-phosphorylated compounds represented by the structure; WHEREIN R and R1 are each members selected from the group consisting of loweralkyl, lower alkoxy, and phenyl; X is sulfur or oxygen; R2 is loweralkyl, loweralkenyl, benzyl, or halosubstituted benzyl; and R3 is a lower alkylene radical, such as methylene, ethylene, lowerlakyl-substituted ethylene, trimethylene, loweralkyl-substituted trimethylene, oxydimethylene, tetramethylene, or loweralkyl-substituted tetramethylene. They find utility as insecticides and arachnicides and are highly effective against both the larval and adult stages of insects.

Unite States Patent 1 Addor et al.

11 3,719,757 1 March 6, 1973 METHOD FOR UTILIZING BISPHOSPHORYLATED IMIDODI- THICARBONATES AS INSECTICIDES OR ARACHNICIDES [75] Inventors: Roger Williams Addor, David Edgar Ailman, both of Pennington, NJ.

[73] Assignee: American Cyanamid Company,

Stamford, Conn.

[22] Filed: May 18, 1972 [21] Appl. No.: 254,522

Related US. Application Data [62] Division of Ser. No. 58,676, July 27, 1970.

[52 US. Cl. ..424/204 [51] Int. Cl. ..A0ln 9/36, AOln 9/00 58] Field of Search ..424/204 [56] I References Cited UNITED STATES PATENTS 2,907,775 10/1959 Dunbar ..260/926 Primary Examiner-Jerome D. Goldberg Assistant Examiner-Allen J. Robinson Attorney-Harry H. Kline [5 7 ABSTRACT Bis-N-phosphorylated compounds represented by the Structure;

Kristin 6 Claims, No Drawings ing the same. More particularly, the invention relates to bis-N-phosphorylated compounds represented by the structure:

it X Sit: Wm

wherein R and R, are each members selected fromthe group consisting of loweralkyl, lower alkoxy and phenyl; X is sulfur or oxygen; R is loweralkyl, loweralkenyl, benzyl or halo-substituted benzyl; and R is a lower alkylene radical, such as methylene, ethylene, loweralkyl substituted ethylene, trimethylene, loweralkyl substituted trimethylene, oxydimethylene, tetramethylene or loweralkyl substituted tetramethylene.

The bis-N-phosphorylated compounds as hereinabove defined 'find utility as insecticides and arachnicides and are highly effective against both the larval an d adultstages of insects, such as the mosquito, and may be used either as contact or systemic insecticides. Among the pests readily controlled with the compounds of the invention are the Southern Armyworm, Bean Aphid, Two-spotted Spider Mite, Large Milkweed Bug, German Cockroach, Southern Corn Roo tworm and House Fly.

' In its'broadest embodiment, the compounds of the present invention are prepared by treating a phosphinyl isothiocyanate with a salt of an alkylene dithiol. Thereafter, the thus formed alkylene-bis-phosphinyl dithiocarbamate is alkylated with an alkyl halide, alkenyl halide, benzyl halide or halo-substituted benzyl halide to obtain the desired alkylene-bis-phosphinylimidodithiocarbonate product.

Alternatively, those compounds in which R, is oxydimethylene are prepared by the reaction of the respective isothiocyanate with an alkali metal hydrosultide to form the corresponding dithiocarbamate salt. This salt is further reacted with bis-chloromethyl ether to form the oxydimethylene bis-phosphinyldithiocarbamate. Treating the resultant mixture with an alkylating agent in the presence of triethylamine results in the formation of the oxydimethylene bis-phosphinylimidodithiocarbonates of the present invention. Each of the compounds thus prepared is highly effective as an insecticide, ara chnicide or nematocide. f 7 In general, the compounds of the present invention having the formula:

wherein R and R, are members selected from the group consisting of loweralkyl, loweralkoxy and phenyl; X is sulfur or oxygen; R, is loweralkyl, loweralkenyl, benzyl or halo-substituted benzyl; and R, is methylene,

ethylene, loweralkyl substituted ethylene,

trimethylene, loweralkyl substituted trimethylene, ox-

ydimethylene, tetramethylene or lower alkyl substituted tetramethylene are prepared in two stages.

First, a phosphinyl isothiocyanate of the formula:

is reacted with the salt of an alkylene dithiol of the formula:

wherein M is an alkali metal, such as sodium, potassium, or lithium, or a trialkylammonium group to form an alkylene-bis-phosphinyldithiocarbamate salt. Upon' acidification the alkylene-bis-phosphinyldithiocarbamate thus formed is recovered. Approximately 2 moles of the isocyanate reactant are used per mole of the alkylene dithiol. However, the molar ratio may be varied somewhat without seriously altering product yield. Advantageously, the reaction can be carried out over a wide range of temperatures, usually between about 0 C. and C., but it is preferred to conduct the reaction at a temperature between about 30 C. and 60 C. Graphically, the over-all reaction may be illustrated as wherein R, R R X and M are as hereinabove defined.

Illustrative of the alkylene-bis-phosphinyldithiocarbamates so prepared are: ethylene-bis-diethoxyphosphinyldithiocarbamate, methylene-bis-dimethoxyphosphinyldithiocarbamate, propylene-bis-diethylphosphinyldithiocarbamate, tetramethylene-bis-dibutoxyphosphinyldithiocarbamate, 1,2-butylene-bis-ethoxy-phenylphosphinyldithiocarbamate, 2,3-butylene-bisdiethoxyphosphinyldithiocarbamate, 2,2-dimethyltrimethylene-bis-methylphenylphosphinyldithiocarbamate, ethylene-bis-diphenylphosphinyldithiocarbamate, methylene-bis-diethoxyphosphinothioyldithiocarbamate, propylene-bis-diethoxyphosphinylimidodithiocarbonate,

' bonate,

. ylimidodithiocarbonate, dimethallyl-diethylphosphinylimidodithiocarbonate,

wherein R, R R X and M are as previously defined, R, is loweralkyl, loweralkenyl, such as allyl or methallyl, benzyl or halo-substituted benzyl, such as 4- iodobenzyl, 2,4-dichlorobenzyl, 3 ,4,S-tribromobenzyl, and Z is a halogen or a p-toluenesulfonate group to form the corresponding alkylene-bis-phosphinylimidodithiocarbonates. The reaction is preferably carried out at about a one to two mole ratio of the alkylene-bis phosphinyldithiocarbamate salt to alkyl halide, respectively.

Typical of the alkylene-bis-phosphinylimidodithiocarbonates of the present invention which may be prepared are: S,S'-ethylene-S,S'-dibenzyldiethoxyphosphinylimidodithiocarbonate, S,S'- ethylene-8,8-dimethyl-diethoxyphosphinylimidodithiocarbonate, S,S-propylene- S,S'-diallyldiethoxyphosphinylimidodithiocarbonate, S,S'- tetramethylene-S,S'-dibutyl methylethoxyphosphin- S,S'- l ,2-butylene-S,S'-di-4- bromobenzyl-dietl'ioxyphosphinylimidodithiocarbonat e, S,S'-2,3-butylene-S,S-di-methallyl-dimethylphosphinylimidodithiocarbonate, S,S'-2,2-dimethyltrimethylene-S,S-diethyl-diethylphosphinylimidodithiocarbonate, S,S'-propylene-S,S'-di-4- chlorobenzyl-methoxyphenylphosphinylimidodithiocar bonate, S,S-ethylene-S,S'-di-2,4-dichlorobenzyldiethoxyphosphinylimidodithiocarbonate, S,S'- ethylene-S,S'-di-2,4,6-trichlorobenzyl-diethoxyphosphinylimidodithiocarbonate, S,S'-ethylene-S,S'-di-2,6- dibromobenzyl-diethoxyphosphinylimidodithiocar- S,S'-trimethylene-S,S-di-2-chlorobenzyldiphenylphosphinylimidodithiocarbonate, S,S'- methylene-8,8'-di-4-iodobenzyl-ethylphenylphosphinylimidodithiocarbonate, S,S-ethylene-S,S'-di.-3- fluorobenzyl diethoxyphosphinylimidodithiocarbonat e, S,S-ethylene-S,S-dimethyl-diphenylphosphinylimidodithiocarbonate, S,S'-ethylene-S,S'-dimethyldiethoxyphosphinylimidodithiocarbonate, S,S'- ethylene-8,8'-dimethyl-diethoxyphosphinothioylimidodithiocarbonate, S,S-trimethylene-S,S'- 3,5-dichlorobenzyl-dimethoxyphosphin- S,S-l,2-butylene-S,S'-

S,S"propylene-S,S-dibenzyldiphenylphosphinylimidodithiocarbonate.

An alternative method of preparing the compounds of the present invention is to treat the phosphinyl isothiocyan-ates of the formula:

with an alkali metal hydrosulfide, MSH, yielding the corresponding phosphinyldithiocarbamate salt:

where R, R and M are hereinabove defined.

Where the latter salt is reacted with bis-chloromethyl ether and the reaction mixture acidified, there are formed oxydimethylene bis-phosphinyldithiocarbamates of the formula:

Illustrative of the oxydimethylene-bis-phosphinyldithiocarbamates so prepared are: oxydimethylene-bisdiethoxyphosphinyldithiocarbamate, oxydimethylenebis-dimethoxyphosphinyldithiocarbamate, ox-

ydimethylene-bis-dimethylphosphinyldithiocarbamate,

oxydimethylene-bis-methoxyethylphosphinyldithiocarbamate, oxydimethylene-bis-diphenylphosphinyl dithiocarbamate.

However, when the latter reaction mixture is not acidified, but is further alkylated, as for example, with an alkyl halide:

the bonates are formed having the formula:

[ yaaasg m wherein R, is a methylene group, it is a good practice to react the above .phosphinyldithiocarbamate salt first an alkylating agent: VJ

wherein R, is as defined above and Z is a halogen atom,

i such as chlorine, bromine or iodine.

Suitable alkylating agents'employed are: methyl iodide, ethyl bromide, ally] chloride, isopropyl iodide, methallyl bromide, butyl iodide,vbenz yl chloride, 4- bromobenzyl chloride, 4-chlorobenzyl chloride, 2,4- dichlorobenzyl chloride, 2,6-dibromobenzyl iodide,

2,4,6-trichlorobenzyl chloride, 2-chlorobenzyl bromide, 3-fluorobenzyl bromide and 4-iodobenzyl iodide.

oxydimethylene-bis-phosphinylimidodithiocar- I The alkylation step is next followed by reaction with a methylene halide, such as methylene bromide or methylene iodide to obtain the corresponding ethylenebis-phosphinylimidodithiocarbonates as written graphi- 2 P-NH-C-SR: CHzZz 213 R1/ 2 wherein B is a base, such as triethylamine, sodium carbonate or potassium hydroxide, and R, R X and Z are the same as defined above.

The invention will be further illustrated in conjunction with the following examples which are to be taken as illustrative only and not by wayof limitation. All parts are by weight unless otherwise stated.

EXAMPLE 1 Preparation of Ethylene-Bis-Diethoxyphosphinyldithiocarbamate The sodium salt of ethanedithiol is obtained as a colorless solid by adding the dithiol to excess sodium methoxide in ethanol under nitrogen followed by addition thereof of benzene. It is washed with ethanolbenzene and then with ether and dried in vacuo. To a cooled (room temperature) mixture of 8.5 parts of diethoxyphosphinyl isothiocyanate in 100 parts (by volume) of benzene is added 3.0 parts of ethanedithiol sodium salt. After an hour, parts (by volume) of the stirred mixture is removed and the very fine solids are spun down in the centrifuge and washed with 1 part of ether. The nuclear magnetic resonance spectrum in deuterium oxide shows a singlet at 6.80 'r (-CH S-, 4H), a multiplet at 5.9 'r (CH -O, 8H), and a doublet at 8.68 r (CH -C, 121-1).

The remainder of the reaction mixture is mixed with water and the phases are separated. The benzene phase is washed several times with water. The combined water fractions are filtered, washed once with ether, poured into a flask, ice-cooled, and acidified with 25 percent hydrochloric acid. The precipitated solids are washed several times with water and vacuum dried at 45 C.-50 C. over potassium hydroxide leaving 8.7 parts (84 percent based on work-up of 90 percent of the intermediate salt) of pale yellow crystals, melting point 115 C.-l 18 C. Recrystallization by dissolving 5.0 parts in ethanol with slight warming followed by dilution with two volumes of hexane and cooling to -20 C. gives 3.4 parts of very fine pale yellow crystals, melting point 120 C.-125 C. at 1/min. (dec.).

Analysis: Calcd. for C12H25NgOaPgs4:

Calcd: C, 29.74; H, 5.29: N, 5.78; P, 12.79; S, 26.47

Found: C, 30.14; H, 5.13; N, 5.75; P, 12,65; S, 26.66

The infrared spectrum shows strong maxima at 1240, 1280, 1480, and 3080 cm", the latter two assignable to the group. The nuclear magnetic resonance spectrum in deuterochloroform shows a doublet at 0.1 'r (J 8 ppm, N-H, 2H), a singlet at 6.40 1' (SCH,, 4H), a multiplet at 5.7 1- (-CH --O, 8H), and a triplet at 8.58 'r (J= 7 ppm, CH -C, 12H).

Utilizing the same procedure employed above to prepare ethylene bis-diethoxyphosphinyldithiocarbamate but with the indicated substitution of reactants, the following analogs are prepared.

A. PREPARATION OF TRIMETHYLENE BIS- DlETI-IOXYPI-IOSPHINYLDITHIOCARBAMATE By substituting propane-1,3-dithiol for ethanedithiol, melting point 89 C.-90 C.

Analysis: Calcd. for C H N O P S Caled: C, 31.31; H, 5.66; N, 5.62; P, 12.42; S, 25.72

Found: C, 31.29; H, 5.84; N, 5.79; P, 12.24; S, 25.48 B. PREPARATION OF PROPYLENE BIS-DIETHOX- YPHOSPl-IINYLDITHIOCARBAMATE By substituting propane-1,2-dithiol for ethanedithiol, melting point 1 14 C.-1 15 C.

Analysis: Calc d. for CyaHgaNgOgPgSqi Calcd: C, 31.31; H, 5.66; N, 5.62; P, 12.42; S, 25.72

Found: C, 31.42; H, 5.80; N, 5.72; P, 12.64; S, 25.91 C. PREPARATION OF ETl-IYLENE BIS-DIETHOX- YPHOSPI-IINOTI-IIOYLDITHIOCARBAMATE By substituting potassium diethoxyphosphinothioyldi-thiocarbamate, melting point C.-1 10 C.

Analysis: Calcd. for CnHggNgOqPgSaI Calcd: C, 27.89; H, 5.07; N, 5.42; P, 11.99; S, 37.24

Found: C, 28.00; H, 5.27; N, 5.60; P, 11.78; S, 37.20 D. PREPARATION OF TRIMETl-IYLENE-BIS- DIETHYLPHOSPHINYLDITHIOCARBAMATE By substituting diethylphosphinyl isothiocyanate for diethoxyphosphinyl isothiocyanate, and trimethylenedithiol sodium salt for ethanedithiol sodium salt, trimethylene-bis-diethylphosphinyldithiocarbamate was obtained in good yield.

E. PREPARATION OF 2,3-BUTYLENE-BIS- ETHOXYPHENYLPI-IOSPHINOTHI YL- DITHIOCARBAMATE Substituting ethoxyphenylphosphinothioyl isothiocyanate for diethoxyphosphinyl isothiocyanate, and 2,3-butanedithiol sodium salt for ethanedithiol sodium salt resulted in the formation of 2,3-butylene-bis-ethoxyphenylphosphinothio ldithiocarbamate in good yield. F. PREPARATION OF TETRAMETHYLENE-BIS- DIPHENYLPI-IOSPHINYLDITHIOCARBAMATE By substituting diphenylphosphinyl isothiocyanate for diethoxyphosphinyl isothiocyanate, and tetramethylenedithiol sodium salt for ethanedithiol sodium salt, tetramethylene-bis-diphenylphosphiny1- dithiocarbamate was obtained in good yield.

EXAMPLE 2 Preparation of S,S'-Ethylene-S,S'-Dibenzy1-Diethoxyphosphinylimidodithiocarbonate To a mixture of 1.48 parts of ethanedithiol and 3.4 parts of triethylamine in 30 ml. of benzene is added, with cooling, 5 .7 parts of diethoxyphosphinyl isothiocyanate. After an hour, this mixture is added to 5.7 parts of benzyl bromide in 25 parts by volume of toluene in several portions over a ten minute period (mild temperature rise to 29 C.). After stirring overnight, the mixture is diluted with more benzene, washed (including dilute sodium hydroxide), and concentrated to give 10.7 parts of oil. Column chromatography on a total of 150 parts of silica gel yields, on

sequential elution with l 1 carbon I tetrachloride:chloroform, chloroform and 2-l0 perrespectively.

By the same procedure used to prepare S,S'-ethylene S ,S'-dibenzy1 diethoxyphosphinylimidodithiocarbonate but with the indicated substitution of reagents, the following analogs are prepared. G. PREPARATION OF S,S-ETHYLENE-S,S'- DIMETHYL-DIETI-IOXYPHOSPHIN- YLIMIDODITHIOCARBONATE By substituting methyl iodide for benzyl bromide, melting point 61 C.-63 C.

Calcd: C, 32.79; H, 5.90; N, 5.47; P, 12.08; S, 25.03

Found: C, 32.76; H, 6.10; N, 5.60; P, 11.87; S, 25.11 H. PREPARATION OF S,S-ETHYLENE-S,S'- DIETHYL-DIETHOXYPHOSPHIN- YLIMIDODITHIOCARBONATE By substituting ethyl bromide for benzyl bromide, melting point 27 C.28 C.

Analysis: Calcd. for C H N- O P,S

Calcd: C, 35.54; H, 6.34; N, 5. 1 8; P, 11.46; S, 23.72

Found: C, 35.52; H, 6.46; N 5.26; P, 11.40; S, 23.72 I. PREPARATION OF S,S-TR1METHYLENE-S,S- DIM ETHYL-DIETHOXYPHOSPHIN- YLIMIDODITHIOCARBONATE By substituting methyl iodide for benzyl bromide and propane-1,3-dithiol for ethanedithiol, there is prepared the above oily compound analyzing as follows:

Calcd: C, 34.21; H, 6.13; N, 5.32; P, 11.76; S, 24.36

Found: C, 34.15; H, 6.13; N, 5.31;P, 11.64; S, 24.47

'J. PREPARATION OF S,S'-PROPYLENE-S,S'-

OTHlOYLIMIDODITHIOCARBONATE By substituting methyl iodide for benzyl bromide and diethoxyphosphinothioyl isothiocyanate for diethoxyphosphinyl isothiocyanate, melting point 76 C.-77 C Analysis: Calc'd. for C,,H N 0,P,S,:

Calcd: C, 30.86; H, 5.55; N, 5.15; P, 11.37; S, 35.32

Found: C, 30.65; H, 5.40; N, 5.13; P, 11.30; S, 35.30 L. PREPARATION OF S,S-ETHYLENE-S,S-DI-4- CHLOROBENZYLDIETHOXYPHOSPHIN- YLIMIDODITHIOCARBONATE By substituting 4-chlorobenzyl iodide for benzyl bromide, the compound S,S'-ethylene-S,S'-di-4- chlorobenzyldiethoxyphosphinylimidodithiocarbonatc was obtained, melting point 7 1.5-73.5 C. Analysis: Calcd. for C H ChN O P sn Calcd: C, 42.56; H, 4.95; CI, 9.66; N, 3.82; P, 8.44;

S, 17.48 Found: C, 42.73; H, 5.24; CI, 9.92; N, 3.93; P, 8.23;

S, 17.20 M. PREPARATION OF S,S'-ETHYLENE-S,S- DIBENZYL-Dlm-PROPOXYPHOSPHIN- YLIMIDODITHIOCARBONATE By substituting di-n-propoxyphosphinyl isothiocyanate for diethoxyphosphinyl isothiocyanate, the

compound S,S'-ethylene-S,S'-dibenzyl-di-n-propoxyphosphinylimidodithiocarbonate was obtained as an oil.

Calcd: C, 49.97; H, 6.43; N, 3.89; P, 8.59; S, 17.79 Found: C, 50.18; H, 6.98; N, 3.86; P, 8.81; S, 17.51 N. PREPARATION OF S,S'-ETHYLENE-S,S- DIBENZYL-DI-i-PROPOXYPHOSPH1N- YLIMIDODITHIOCARBONATE By substituting di-i-propoxyphosphinyl isothiocyanate for diethoxyphosphinyl isothiocyanate, the compound S,S'-ethy1ene-S-,S'-dibenzyl-di-i-propoxyphosphinylimidodithiocarbonate was obtained in good yield.

Analysis: Calcd. for C3oH4 N205PzS41 Calcd: C, 49.97; H, 6.43; N, 3.89; P, 8.59; S, 17.79

Found: C, 49.83; H, 6.51; N, 3.93; P, 8.08; S, 18.02 0. PREPARATION OF S,S'-TRIMETHYLENE-S,S'- DIBENZYL-DIETHOXYPHOSPHIN- YLIMIDODITHIOCARBONATE By substituting propane-1,3-dithiol for ethanediol, the compound S,S'-trimethy1ene-S,S-dibenzyldiethoxyphosphinylimidodithiocarbonate was obtained as an oil.

Analysis: Calc'd. for C, l-I,,,N,O P,S,:

Found: C, 47.51; H, 6.04; N, 4.22; P, 9.26; S, 19.16 P. PREPARATION OF S,S-ETHYLENE-S,S- DIBENZYL-DIETHOXYPHOSPHIN- 0THIOYLIMIDODITHIOCARBONATE By substituting diethoxyphosphinothioyl isothiocyanate for diethoxyphosphinyl isothiocyanate, the compound S,S'-ethylene-S,S'-dibenzy1-diethoxyphosphinothioylimidodithiocarbonate was obtained in good yield.

Analysis: CalCd. fOl' CgaHagNgO PgSgi Calcd: C, 44.81; H, 5.50; N, 4.02; P, 8.89; S, 27.61

Found: C, 44.89; H, 5.68; N, 4.06; P, 8.75; S, 27.69 O. PREPARATION OF S,S-TETRAMETHYLENE- S,S'-DIBENZYL-DIETHOXYPHOSPHIN- YLIMIDODITHIOCARBONATE By substituting butane-1,4-dithio1 for ethanediol, the compound S,S'-tetramethylene-S,S'-dibenzyl-diethoxyphosphinylimidodithiocarbonate was obtained as an oil.

Analysis: Cale dfor CggH42N20qP2S4I Calcd: C, 48.54; H, 6.10; N, 4.04; P, 8.94; S, 18.51

Found: C, 48.80; H, 5.74; N, 4.29; P, 8.64; S, 18.3] R. PREPARATION OF S,S'-2,2-DIMETHYL- TRIMETHYLENE-S,S'-DI-2,4-DICHLOROBENZYL- DIMETHYLPHOSPHINYLIMIDODITHIOCAR- BONATE Substituting neopentyldithiol for ethanediol; dimethylphosphinyl isothiocyanate for diethoxyphosphinyl isothiocyanate; and 2,4-dichlorobenzyl chloride for benzyl bromide, the compound S,S-2,2-dimethyl- 9 trimethylene-S,S'-di-2,4-dichlorobenzyl-dimethylphosphinylimidodithiocarbonate was obtained in good yield.

S. PREPARATION OF S,S'-PROPYLENE-S,S'-DI-4- FLUOROBENZYLETHYLETI-IOXYPHOS- PHINOTl-lIOYLIMIDODITHIOCARBONATE Substituting propane 1,2-dithiol for ethanediol', ethylexthoxyphosphinothioyl isothiocyanate for diethoxyphosphinyl isothiocyanate; and 4-fluorobenzyl iodide for benzyl bromide, the compound S,S'- propylene-8,8-di-4-fluorobenzylethylethoxyphosphinothioylimidodithiocarbonate was obtained. T. PREPARATION OF S,S'-TRlMETl-IYLENE-S,S'- DI-2-BROMOBENZYLETI-lOXYPl-IENYLPl-IOS- PHlNYLIMIDODITHlOCARBONATE Substituting propane 1,3-dithiol for ethanediol; ethoxyphenylphosphinyl isothiocyanate for diethoxyphosphinyl isothiocyanate; and 2-bromobenzyl bromide for benzyl bromide, the compound S,S'- trimethylene-5,8-di-2-bromobenzyl ethoxyphenylphosphinylimidodithiocarbonate was obtained. U. PREPARATION OF S,S'-1,2-BUTYLENE-S,S'-DI- 2-Cl-ILORO-4-lODOBENZYL-DIMETl-IOXYPl-IOS- PHINYLIMIDODITHIOCARBONATE Substituting butane-1,2-dithiol for ethanediol; dimethoxyphosphinyl isothiocyanate for diethoxyphosphinyl isothiocyanate; and 2-chloro-4-iodobenzyl chloride for benzyl bromide, the compound S,S'-1,2- butylene-S,S'-di-2-chloro-4-iodobenzyI-dimethoxyphosphinylimidodithiocarbonate was obtained. V. PREPARATION OF S,S'-2,3-DIMETHYL- TETRAMETI-IYLENE-S,S'-DI-2METHALLYL- DIETHOXYPl-IOSPHIN- YLIMIDODITHIOCARBONATE Substituting 2,3-dimethylbutane-1,4-dithiol for ethanediol, and methallyl chloride for benzyl bromide, the compound S,S'-2,3-dimethyltetramethylene-S,S'- di-2-methalIyl-diethoxyphosphinylimidodithiocarbonat e was obtained.

EXAMPLE 3 Preparation of 8,5 -Methylene-S,S '-Dimethyl-Diethoxyphosphinylimidodithiocarbonate To 9.6 parts of methyl diethoxyphosphinyldithiocarbamate and 4.0 parts of triethylamine in 32 parts by volume of benzene is added 5.4 parts of methylene iodide. The reaction mixture, after stirring overnight, is water-washed, and concentrated in vacuo. The oil, in methanol, stood several hours to remove the byproduct, diethoxyphosphinyl isothiocyanate. The methanol is removed and the oil in benzene is rewashed. Removal of solvent leaves 8.6 parts of an oil which is further purified by column chromatography on silica gel. The product, recovered from the column with chloroform-methanol, is crystallized from ether at 20 C. to C. to give two crops of white crystals totaling 4.2 parts, melting point 33 C. -34.5 C. and 32.5 C.-33.5 C., respectively.

Analysis: Calcd. for C, l-I, N',0,P,S

Calcd: C, 31.32; H, 5.66; N, 5.62; P, 12.42; S, 25.73

Found: C, 31.28; H, 5.66; N, 5.50; P, 12.30; S, 25.75

The infrared spectrum shows maxima at 1250 cm and 1550 cmattributable to the P=O and C=N functions, respectively EXAMPLE 4 Preparation of Oxydimethylene-bis-Diethoxyphosphinyldithiocarbamate To an ice-cooled mixture of 0.9 part of bischloromethyl ether in 10 parts (by volume) of dry acetone is added 2.0 parts of potassium diethoxyphosphoryldithiocarbamate. After 30 minutes, the bath is removed and the mixture is stirred overnight. Filtration followed by concentration in vacuo gives 1.6 parts of yellow solids. The solids crystallize at room temperature from about 3:1 hexane-chloroform as pale yellow crystals, melting point 98.6 C.-99.6 C., 1.1 parts (58 percent).

Analysis: Calc'd. for c,,I-I N,O-,P,S

Calcd: C, 28.79; H, 5.24; N, 5.60; P, 12.38; S, 25.62

Found: C, 28.61 H, 5.30; N, 5.75; P, 12.12; S, 25.63

The infrared spectrum shows bands at 1480 cm and 3050 cm" attributable to the group and at 1240 cm for the P=O function.

Substituting potassium ethoxyphenylphosphoryldithiocarbamate for the potassium diethoxyphosphinyldithiocarbamate results in the formation of the compound oxydimethylene-bis-ethoxyphenylphosphinyldithiocarbamate.

Advantageously, the compounds may be employed for such pest control in liquid or solid formulations as sprays, dusts, dust concentrates, wettable powders, granular products, organic liquid formulations and emulsifiable concentrates. Solid formulations may be prepared by admixing the active materials with diluent carriers, such as talc, attapulgite, kaolin, diatomaceous earth, fullers earth, and the like, with or without the addition of adjuvants, such as emulsifiers, surfactants, spreading and sticking agents. Liquid formulations, on the other hand, may be prepared by dissolving or dispersing the active material in water or in an organic solvent, generally with a small amount of emulsifier and then dispersing, dissolving, or diluting further the thus formed concentrate just prior to application. Diluents,

such as water, and inexpensive organic solvents, such as fuel oils, deodorized kerosene, and the like, are conventional diluents frequently used for the above purpose.

In the example-below, there is summarized outstanding insecticidal activity, attributed to the compounds of the invention.

EXAMPLE 5 Procedures for the Determination of Insecticidal Activity Southern Armyworm (Prodenia eridania Cramer) Compounds to be tested are made up as 0.1 and 0.01 percent solutions or suspensions in 65 percent acetone/35 percent water mixtures. Sieva lima bean leaves are dipped in the test solutions and set in a hood on a screen to dry. When dry, each leaf is placed in four-inch petri dishes which have a moist filter paper in the bottom, and ten third-instar armyworm larvae about inches long are added to each dish. The dishes are covered and held at F., and 60 percent R.H. After two days, mortality counts and estimates of the amount of feeding are made. The results are reported in Table 1 below. Bean Aphid (Aphisfabae Scopoli) Compounds are tested as 0.1, 0.01, and 0.001 percent solutions or suspensions in 65 percent acetone/35 percent water mixtures. Two-inch fiber pots, each contwo days at 80 F., 60 percent R.H., and the adult mite emulsifier, acetone, and water. This is diluted with suffolded are cut off just above soil level and inserted into R.H., mortality estimates are made and one leaf from 40 tom of a petri dish. Ten third-instar southern arare reported in Table 1 below.

- 3,719,757 ll taining a nasturtium plant 2 inches high and infested 3 with about 150 aphids two days earlier, are sprayed with test solution to give complete coverage of the aphids and the plants. The sprayed plants are laid on their sides on white enamel trays which have had the 5 edges coated with No. 50 SAE oil as a barrier. Mortality estimates are made after holding for two days at 70 F., and 50 percent RJ-l. The results are reported in m Table 1 below. Two-spotted Spider Mite (Tetranychus urticae Koch) Sieva lima bean plants with primary leaves three to four inches long are infested with about 100 adult mites per leaf 4 hours before use in this test. The mite and egg infested plants are'dipped for 3 seconds in the 0.01 and 0.001 percent solutions used in the armyworm tests, c o and the plants set in the hood to dry. They are held for lhsJa.

Root worms lbsJa.

Housefly p.p.m p. p.111. p.p.m.

mortality estimated on one leaf under a stereoscopic microscope. The other leaf is left on the plant an additional five days and then examined at 10X power to estimate the kill of eggs and of newly-hatched nymphs, giving a measure of ovicidal and residual action, respectively. The results are reported in Table 1 below. Systemic Tests The compounds to be tested are fon'nulated as emulsions containing 0.1 gram of test material, 0.2 gram of Systemics Armyworms 10 100 p.p.m. p.p.rn.

ficient water to give l00 ppm and 10 ppm emulsions. Sieva lima bean plants with only the primary leaves un two-ounce bottles of test emulsions and held in place 1 by a bit of cotton wrapped around the stem. The bottles are then placed in a ventilated box with the leaves extending outside the box, such that any possible fumes 5 from the compounds will be drawn out theend of the box rather than rising to affect the test leaves. About fifty adult two-spotted spider mites are placed on each leaf. After holding three days at 80 F. and 60 percent Table l Mites each plant is placed on a moist filter paper in the bot- Aphids mywonn larvae are added to each dish and mortality counts are made after holding another three days at 80 F. and 60 percent R.l-l. The results are reported in Table 1 be w:

l-lousefly (Musca domestica Linnaeus) Groups of 25 adults female houseflies are lightly anesthetized with carbon dioxide, placed in widemouth pint mason jars, and covered with a screen cap. The test compound is formulated as an emulsion containing 50 ppm or 5 ppm of test material, an emulsifier, acetone and water. The mouth of the vial is covered with a single layer of cheesecloth, inverted and placed on the screen cap, so that the flies can feed on the solu? tion through the screen. Mortality counts are made after 2 days at 80 F. the results are reported in Tablel be o V. Southern Corn Rootworm (Diabmtica imdem'mpuncmm howardi Barber) The compound is formulated as a dust and incor porated into the soil at the equivalent of 50 and 10 pounds per acre. The soil is sub-sampled into bottles, andten '6- to 8-day old rootworrn larvae added to each bottle, which is then capped. Mortality counts are made after 6 daysat F., 60 percent RH. the results Armyworm Structure We claim 1. A method for controlling insect and arachnid which comprises applying to said insects or arachnids an insecticidally or arachnicidally effective amount of the compound of the formula:

2. The method according to claim 1 wherein the compound is S,S'-trimethylene-S,S'-dibenzyl-diethoxyphosphinylimidodithiocarbonate.

3. The method according to claim I wherein the compound is S,S-ethylene-S,S'-dibenzyl-diethoxyphosphinylimidodithiocarbonate.

trimethylene, tetramethylene, loweralkyl-substituted;

tetramethylene, or oxydimethylene.

4. The method according to claim 1 wherein the compound is S,S'-methylene-S,S'-dimethyl-diethoxyphosphinylimidodithiocarbonate.

5. The method according to claim 1 wherein the compound is S,S'-tetramethylene-S,S'-dibenzyldiethoxyphosphinylimidodithiocarbonate.

6. The method according to claim 1 wherein the compound is S,S-methylene-S,S-dibenzyl-diethoxyphosphinylimidodithiocarbonate. 1

t tt ti: 

1. A method for controlling insect and arachnid which comprises applying to said insects or arachnids an insecticidally or arachnicidally effective amount of the compound of the formula: wherein R and R1 are each members selected from the group consisting of loweralkyl, loweralkoxy, and phenyl; X is either sulfur or oxygen; R2 is loweralkyl, loweralkenyl, benzyl, or halo-substituted benzyl; and R3 is methylene, ethylene, loweralkyl-substituted ethylene, trimethylene, loweralkyl-substituted trimethylene, tetramethylene, loweralkyl-substituted tetramethylene, or oxydimethylene.
 2. The method according to claim 1 wherein the compound is S,S''-trimethylene-S,S''-dibenzyl-diethoxyphosphinylimidodithiocarbonate.
 3. The method according to claim 1 wherein the compound is S,S''-ethylene-S,S''-dibenzyl-diethoxyphosphinylimidodithiocarbonate.
 4. The method according to claim 1 wherein the compound is S,S''-methylene-S,S''-dimethyl-diethoxyphosphinylimidodithiocarbonate.
 5. The method according to claim 1 wherein the compound is S,S''-tetramethylene-S,S''-dibenzyl-diethoxyphosphinylimidodithiocarbonate. 